Light-sensitive color photographic elements with improved image quality

ABSTRACT

A multi-layer color photographic element comprising a support having a plurality of silver halide emulsion layers, at least one layer being a red-sensitive silver halide emulsion layer, containing a cyan-forming coupler, such as phenol derivatives and Alpha -naphthol derivatives which have an iodine or a bromine atom at the &#39;&#39;&#39;&#39;para&#39;&#39;&#39;&#39; position to the hydroxyl group. Greensensitive emulsion layers and blue-sensitive emulsion layers are generally used in combination with said red-sensitive layer. The order of application of said layers is of no importance, as long as the red-sensitive emulsion layer is separated from different emulsion layers by an intermediate layer containing silver halide grains of reduced photo-sensitivity. Specific examples of the cyan-forming coupler and acceptable silver halide materials are defined in the disclosure.

United States Patent Oishi et a1. Feb. 5, 1974 [54] LIGHT-SENSITIVECOLOR 3,364,022 1/1968 Barr 96/ 100 PHOTOGRAPH: ELEMENTS WITH 3,488,1931/1970 Eynde et a1 96/74 IMPROVED IMAGE QUALITY 3,591,383 7/1971 Yoshldaet a1 96/22 [75] Inventors: Yashushi Oishi; Yoshinobu Yoshida; PrimaryExaminer-J, Travis Brown Kalllya of Karlagawa, AssistantExaminer-Richard L. Schilling Japan Attorney, Agent, or Firm-Sughrue,Rothwell, Mion, 73 Assignee: Fuji Photo Film 00., Ltd, Minami MacpeakAshigara-shl, Kanagawa, Japan ABSTRACT [22] Flled: 1971 A multi-layercolor photographic element comprising [21] APPL 2 355 a support having aplurality of silver halide emulsion layers, at least one layer being ared-sensitive silver Related Apphcat'on Dam halide emulsion layer,containing a cyan-forming cou- Continuation Of ly 1 1968. pler, such asphenol derivatives and a-naphthol derivabandonedatives which have aniodine or a bromine atom at the o para position to the hydroxyl group.Green-sensitive 1 Foreign Appllcatlon Priority Data emulsion layers andblue-sensitive emulsion layers are 7 July18,T% Japan 46-217 generallyused in combination with said red-sensitive layer. The order ofapplication of said layers is of no [52] US. Cl 96/74, 96/22, 96/100importance, as long as the red-sensitive emulsion layer [51] Int. ClG03c 1/76, G03c 3/00 is separated from different emulsion layers by aninter- [58] Field of Search 96/74, 100, 55,22 mediate layer containingsilver halide grains of reduced photo-sensitivity. Specific examples ofthe cy- [56] References Cited an-forming coupler and acceptable silverhalide mate- UNITED STATES PATENTS rials are defined in the disclosure.

3,152,907 10/1964 Godowsksy et a1 96/74 9 Claims, 3 Drawing Figures FilmE Green Density 7 Blue Density Density Red Density memoir-1B w 3;790.3e4

v Film E -Green Density 5 t Blue Density v Density Red Density O 2:0

Film F f1 J? T 'Nreen Density NW Density LO Density Red Density ILIO 26Film G 1 \Green Density l.O \lue Density INVENTORS' Red Density L O. 2:0Yasush/ 0/s/7/ YOsh/hobu flash/bio Kazuya 5000 A RNEYS DensityLIGHT-SENSITIVE COLOR PHOTOGRAPHIC ELEMENTS WITH IMPROVED IMAGE QUALITYThis is a Continuation, of application Ser. No. 745,885, filed July 18,1968, now abandoned.

BACKGROUND OF THE INVENTION 1. Field of the Invention The presentinvention relates to color photography and, more particularly, to alight-sensitive color photographic element having an intermediate layerwhich prevents interlayer migration of a development inhibitingsubstance.

Description of the Prior Art In the formation of color images inmultilayer color photographic elements, a color reproduction process isusually employed in which couplers have been incorporated in differentlysensitized silver halide emulsion layers. On development of the silverhalide, the couplers form color images, in accordance with the silverimage, by reaction with the oxidation product of aromatic primary aminodevelopers, which are commonly used.

Among the couplers employed in such a multilayer system, a cyan couplercarrying an iodine or a bromine atom at the coupling site is sometimesof a great value, because the coupler, on reaction with the oxidizeddeveloper, releases iodide or bromide ions which are, for the most part,captured by near-by silver halide grains and retard excessive reductionof these grains. This effect enables one to control photographicgradation and to improve sharpness and graininess without loweringsensitivity.

However, when this kind of coupler is used in a multilayer material andis present in an emulsion layer which is adjacent a differentlysensitized colonforming layer, a part of the iodide or bromide ionliberated during the coupling reaction migrates from its original layerand retard the development of the adjacent layer as well. This givesrise to an undesirable effect on the gradation of the latter layer,leading to deterioration of color reproducibility.

SUMMARY OF THE INVENTION It has now been found that deterioration inmultilayer color emulsions due to migrating bromide or iodide ions canbe prevented by inserting an intermediate layer between adjacentemulsion layers/Silver halide grains of low photosensitivity areincorporated in the intermediate layer which will capture the migratingbromide or iodide ions, thus insulating any other emulsion layers fromthe halide-releasing layer. The silver halide grains in the intermediatelayer are not reduced during photographic development.

Generally, the multi-layer color photographic element of the inventioncomprises a support having coated thereon a red-sensitive silver halideemulsion layer, a green-sensitive emulsion layer and a bluesensitiveemulsion layer. Since the red-sensitive silver halide emulsion layercontains a cyan-forming coupler, such as phenol derivatives,a'Ipha-naphthol derivatives, each having an iodine or a bromine atompara to the hydroxyl group thereof, it is necessary that the redsensitive silver halide emulsion layer be separated from any greenorblue-sensitive emulsion layer by an intermediate silver halide layer oflow photo-sensitivity which will prevent harmful migration.

The cyan-forming coupler may be selected from compounds having thegeneral formula:

CON

NHCOR2 wherein X is a member selected from the group consisting of aniodine atom and a bromine atom, R CO is an acyl group containing atleast nine carbon atoms, and R and R are each a member selected from thegroup consisting of a hydrogen atom, a halogen atom and an alkyl group.

The silver halide may generally be silver chloride, silver bromide,silver chlorobromide and silver iodobromide.

An object of the present invention is to provide a multi-layer colorphotographic light-sensitive element having an emulsion layer containinga color-forming compound which carries an iodine atom or a bromine atomat the coupling position thereof, and releases iodide or bromide ionsduring its reaction with the oxidation product of an aromatic primaryamino developing agent, said element being provided with an intermediatelayer so that the inter-layervmigration of the iodide ion or bromide ioninto other emulsion layers is effectively prevented.

Another object of this invention is to provide a multilayer colorphotographic material having excellent definition and colorreproduction.

DESCRIPTION OF THE DRAWINGS FIG. 1 is a plot of red color density versusboth green and blue color density for Film E.

FIG. 2 is a plot of red color density versus both green and blue colordensity for Film F.

and blue density for Film G.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention consistsof a multi-layer color photographic element characterized by thepresence of an intermediate layer containing a silver halide emulsion oflow photosensitivity. This intermediate layer lies FIG. 3 is a plot ofred color density versus both green between a silver halide emulsionlayer containing a coupler and another silver halide emulsion containinganother cyan-forming phenol or a-naphthol coupler that carries an iodineor a bromine atom at the coupling site.

The composition of the silver halide to be employed in said intermediatelayer depends on the substituent of the cyan-forming coupler which isemployed. For example, when the substituent of the cyan-forming coupleris iodine, there may be employed silver iodobromide, silver bromide,silver chloro-bromide or silver chloride. This silver halide is notripened because no photosensitivity is required of it. The amount of thesilver halide to be added depends upon the amount of liberated iodide orbromide ion. In normal multi-layer color photographic light-sensitiveelements, l X mols to 1 X 10* mols per 100 sq. cm. of the colorphotographic element is sufficient.

In order to assure the sharpness of the images of the color photographiclight sensitive element, it is desirable that the silver halide grainsof the intermediate layer be substantially transparent. Thus, smallersize silver halide grains are preferred, in particular, 0.5 microns orless in diameter are preferred.

The low-sensitivity silver halide incorporated in the intermediate layeris not developed during the developing process, and it is removed byfixing.

The cyan-forming coupler used in the color photographic light-sensitiveelement is a phenol or naphthol derivative having an iodine or a bromineatom para to the hydroxyl group, and usually it will have a ballastinggroup with more than eight carbon atoms ortho to the hydroxyl group torender the coupler fast to diffusion. Typical examples of thecyan-forming coupler used in this invention are illustrated below:

OONHCizHzs n 0H M M h CONHCnH CONH(CH1)BOQCBHU(Q sHn(t) Ivy... OH WoonmcmmQcmm) V sHn) (v on 00Nncmonmcmcnmn00- IOCHIIH miii ss- C O NHCHCHgNHC 0 CH0 "H" T EDT h i i afiii OH N SOaH N vm). 0H

01- Imrcomno-Q-cnmo) CH1 11111) 01 NHCOOHO- 05m) $2116 CH: a iK X OH WWCl NHCONHCuHn These cyan-forming couplers are conveniently obtained byintroducing an iodine atom or a bromine atom into the 4-position of acorresponding 2- substituted naphthol or phenol by direct halogenationor by a Sandmeyer reaction. Examples of methods of preparation of thesecyan-forming couplers are shown below.

1. Preparation of l#hydroxy-4-iodo-N-n-dodecyl-2- naphthamide:

CONHCuI-Iu To 500 ml. of glacial acetic acid were added g. ofl-hydroxy-N-n-dodecyl-2-naphthamide, 28 g. of anhydrous sodium acetate,and 35 g. of anhydrous lead acetate. The mixture was heated to 70-80C.and there was added (dropwise) 50 g. of a saturated methanol solution of50 g. of iodine over a 3 hour period while stirring and irradiating withsun light. After an additional hour, the product was filtered, thefiltrate was cooled, and the crystals that deposited were collected. Thecrystals were then recrystallized from acetone and dried thoroughly. Theyield of the product, melting at 93-94C., was 32 g.

Couplers 11, V, Vll and Vlll may also be prepared from the correspondingcompounds by a similar procedure.

2. Preparation of 1-hydroxy-4-bromo-N-n-dodecyl-2- naththamide:

CONHCuHzs To 500 ml. of methylene chloride was added 70 g. ofl-hydroxy-N-n-dodecyl-Z-naphthamide. While stirring the solution undercooling conditions, 100 ml. of a methylene chloride solution of 32 g. ofbromine was added dropwise over a 2 hour period. The system was thenstirred for an additional 30 minutes, whereupon the crystals of thecoupler precipitated and were collected. The filtrate was concentratedto 150 ml. and cooled to separate a second crystal crop. The two cropswere combined and recrystallized twice from methanol to provide 70 g. ofpure product melting at 97C.

Couplers IV, VI, 1X and X may be prepared similarly from thecorresponding compounds by brominating in methylene chloride.

These couplers may be incorporated in the cyanforming emulsion layereither by themselves or as a mixture thereof, or in a mixture withconventional cyan-forming couplers having no halogen atom. Moreover, byadjusting the mixing ratio of these couplers, image definition can becontrolled.

The invention will be explained in more detail by the followingexamples, although the invention should not be limited thereby.

EXAMPLE 1 The following three types of photographic films were prepared:

Film A In a mixture of 10.0 ml. of tri-o-cresylphosphate and 7.0 ml. ofethyl acetate there was dissolved 5 g. of 1-hydroxy-4-iodo-N-n-dodecyl-naphthamide (Coupler l). The resultingsolution was dispersed in 50 ml. of a percent aqueous gelatin solutioncontaining 4 ml. of a 5 percent aqueous solution of sodiumn-dodecylbenzenesulfonate. Twenty-one g. of the emulsion formed wereadded to 100 g. of a red sensitive silver halide emulsion containing 5.0g. of gelatin and 3.0 X 10' moles of silver iodo-bromide, and theresultant emulsion was applied to a cellulose triacetate film at a drythickness of 5 microns. To the surface of the thus formed emulsion layerwas applied an emulsion of fine silver bromide particles, which had notbeen chemically ripened, at a dry thickness of 1.5 microns, so that 4X10 moles of silver bromide were contained in 100 sq. cm. of the layer.To the surface of this intermediate layer were successively applied agreen-sensitive silver iodobromide emulsion containing, as amagentaforming coupler, l-(2', 6'-dichloro-4'-methoxy)-3- 3II[a (2I!I4'-di-tert-amylphenoxy)-butyramido]phenylureido- S-pyrazolone, adispersion of yellow colloidal silver, and a blue-sensitive emulsioncontaining as a yellow coupler a- 3-[a-(2, 4"-di-tert-amylphenoxy)-acetamido1-benzoyl -2-methoxyanilide. The final product was labeled FilmA.

Film B A multi-layer color photographic film having the same layerstructure as Film A was prepared in the same manner as Film A, with theexception that the intermediate layer, the red-sensitive emulsion layerand the green-sensitive layer contained no silver bromide.

Film C A multi-layer color photographic film which otherwise was thesame as Film A was prepared without an intermediate layer between thered-sensitive emulsion layer and the green-sensitive one.

These films, after exposure, were developed in a color developer (pl-l10.8) containing as a developing agentN-ethyl-N-(fl-sulfoamidoethyl)-3-methyl-4- aminoaniline sulfate, for 14minutes at 21C. These films were then subjected to conventional fixing,bleaching, fixing again and washing to provide colored films.

Film A, Film B, and Film C were each exposed to blue light, green lightand to red light separately, through an optical wedge. They were thensubjected to a development process in order to provide the gradationsshown in the following table, which correspond to the gradation of eachlight sensitive emulsion layer of the multi-layer color photographicfilm.

Table 1 Gamma-Values (separate exposure) Density measured Coupling layerFilm A B C Blue density Blue sensitive 1.25 1.20 1.22 Green densityGreen sensitive 1.30 1.35 1.30 Red density Red sensitive 1.45 1.40 1.40

Table 2 Gamma-values (white-light exposure) Density measured Couplinglayer Film A B C Blue density Blue sensitive 1.20 1.20 1.15 Greendensity Green sensitive 1.20 0.90 0.85 Red density Red sensitive 1.221.20 1.25

The above results show that when the films were exposed separately(three-color exposure) followed by light, the gradations of thegreen-sensitive layer of Film B and C were greatly reduced, and that thegradations of the blue-sensitive layer and the red-sensitive layer wereunbalanced, resulting in improper color reproduction. On the other hand,Film A, having the intermediate layer of this invention, showed thecorrect color reproduction and was free from any disturbance in thegradation of the green-sensitive layer due to the coupling in thered-sensitive layer.

Another film, Film D, having the same layer structure as Film A wasprepared using as the cyan-forming couplerl-hydroxy-4-chloro-N-ndodecyl-2-naphthamide, and the granularity of thecyan image was compared in both cases. The results showed that Film A ofthis invention was superior in granularity and definition to Film D.

EXAMPLE 2 The following three kinds of films were prepared:

Film E A blue-sensitive silver chloro-bromide emulsion containing as ayellow-forming coupler abenzoyllZ-methoxyanilide was applied to a filmbase. To the surface of the emulsion layer formed there was applied asuperfine emulsion of silver chloride, which had not been chemicallyripened, at a dry thickness of 1 micron and at 2 X 10" mole-silver/lsq.cm., to provide an intermediate layer.

In a mixture of 10 ml. of di-n-butyl phthalate and ml. of ethyl acetatethere was dissolved 5.0 g. of lhydroxy-4-bromo-N-n-dodecyl-2-naphthamide(Coupler ll), and the resulting solution was dispersed in 50 ml. of apercent aqueous solution containing 4 ml. of a 5 percent aqueoussolution of sodium n-dodecyl sulfonate to provide a coupler emulsion.The coupler emulsion g.) was added to 100 g. ofa red-sensitive emulsioncontaining 5.0 g. of gelatin and 2.0 X 10 moles of silverchloro-bromide. The mixture was applied to the surface of theintermediate layer at a dry thickness of 5 microns. To the surface ofthe emulsion layer there was applied a second intermediate layer havingthe same composition as the first intermediate layer, and to the surfaceof the second intermediate layer, there was further applied agreen-sensitive silver chloro-bromide emulsion containing as amagentaforming coupler l-(2,6-dichloro-4-methoxy)-3- {3'- [a- (2"4"-di-tertamylphenoxy)-butylamido] plienylureido}-5-pyrazqlone.

Film F t A multi-layer color photographic film having the same layerstructure as Film E was prepared. However, the two intermediate layersadjacent the red-sensitive emulsion layer contained no silver chloride.

Film G A multi-layer color photographic film having the same layerstructure as Film E was prepared, except that no intermediate layerswere provided.

After exposure, the films were developed in a color developer containingas a developing agent N,N-

were subjected to standard fixing, bleaching, fixing and washingutilized to provide color films.

Two samples were prepared from each of the films, i.e., two strips werecut from each of Films E, F and G. The filmswere initially exposed tored light under an optical wedge. Then, uniform blue and greenirradiation of intermediate intensity was given to one strip and theother, respectively. The films were then developed and the blue, greenand red density values thereof were measured. The relationship of thesedensity values is shown in FIGS. 1, 2 and 3 of the accompanyingdrawings. The results show that while Film F and Film G had beenuniformly exposed to green and blue light, respectively, these samplesshowed no uniformity in the green and blue sensitive layers due to thedevelopmentinhibiting influence of the red-sensitive layer. On the otherhand, Film E of this invention showed the correct green density and thecorrect blue density corresponding to the exposure.

Another film, Film H, having the same layer construction as Film E wasprepared using, as a cyanforming coupler,l-hydroxy-4-chloro-N-n-dodecyl-2- naphthamide. Film H and Film E wereeach closely contacted with a negative color image, and were processedto provide positive images, which, on projection, showed that Film Egave a finer and sharper cyan projection than Film H.

EXAMPLE 3 The following three kinds of multi-layer color photographicfilms were prepared:

Film I In a mixture of 10.0 ml. of tri-o-cresyl phosphate and 7.0 ml. ofethyl acetate were dissolved 2.5 g. oflhydroxy-N-n-dodecyl-2-naphthamide and 2.5 g. oflhydroxy-4-iodo-N-n-dodecyl-2-naphthamide. The resulting solution wasdispersed in 50 m1. of a 10 percent aqueous gelatin solution, containing4 ml. of a 5 percent aqueous solution of sodiumn-dodecyl-benzenesulfonate, to provide an emulsion. The emulsion (25 g.)was added to l00 g. of a red-sensitive silver halide emulsion containing5.0 g. of gelatin and 3.0 X 10' moles of silver iodo-bromide. The silverhalide emulsion thus prepared was applied to a cellulose triacetate filmat a dry thickness of 5 microns. On the surface of the silver halideemulsion layer thus formed, there was applied an emulsion of fine silverchloride grains, which had not been chemically ripened, at a drythickness of 1.5 microns so that 5 X 10" moles of silver chloride werecontained per 100 sq.cm. of this intermediate layer. To this layer wereapplied, successively, a greensensitive silver iodo-bromide emulsioncontaining, as a magenta-forming coupler, l-(2', 6-dichloro-4-methoxy)-3-3"-[a-2", 4"-di-tert-amylphenoxy)-butyramido]phenylureido-5-pyrazolone and then a blue-sensitive emulsion con- I taining, as ayellow-forming coupler, a-l3'-[a-(2", 4"-

10.7) for 14 minutes at 21C. Thereafter, the films Idi-tert-amylphenoxy)-acetamido]-benzoyl} -2-r r ethoxyanilide, as inExample 1.

Film J A multi-layer color photographic film having the same layerconstruction as Film l was prepared, except that the intermediate layerbetween the red-sensitive emulsion layer and the green-sensitiveemulsion layer was a gelatin layer of 1.5 microns thickness containingno i ri shlq d Film K A multi-layer color photographic film having thesame layer structure as Film 1, except that no intermediate layer wasprovided between the red-sensitive emulsion layer and thegreen-sensitive emulsion layer, was prepared.

Each of Films 1, J and K thus prepared was exposed separately to bluelight, green light and red light, under an optical wedge, and developedin a color developer containing, as a developing agent, N-ethyl-N-(B-methane-sulfoneamidoethyl)-3-methyl-4-aminoaniline sulfate (pl-l=l0.8)for 14 minutes at 21C., and subjected to fixing, bleaching, fixing andthen washing to provide a film with the gradations shown in the Table Esrad tiqa r nq ils KQBBQWEFILWQHHPE obtained by separate development ofeach silver halide layer in these multilayer photographic films.

Table 3 Gamma-values (separate exposure) Density measured Coupling LayerFilm l J K Blue density Blue sensitive l.l2 l.l Green density Greensensitive 1.22 l.l9 Red density Red sensitive .29 1.28

ln another experiment, Films 1, J and K were exposed to white lightunder an optical wedge, and were developed as in Example 1 to providethe gradations which are shown in Table 4. A as.

Table 4 Gamma-values (white-light exposure) Density measured Couplinglayer Film Blue density Blue sensitive .10 L07 1.06 Green density Greensensitive 1.18 1.01 1.00 Red density Red sensitive 1.20 L2] 1.19

the green-sensitive emulsion layer was not disturbed by the coupling inthe red-sensitive emulsion layer and a correct color reproduction wasobtained.

Another multi-layer color photographic film (Film L) having the samelayer structure as Film I was prepared, using as the cyan-formingcoupler'l-hydroxy-N- n-dedecyl-Z-naphthamide. After exposing anddeveloping, the granularity of images was compared between Film l andFilm L. Film I showed finer granularity and better definition than FilmL.

What is claimed is:

1. In a multi-layer color photographic element com-' prising a supporthaving coated thereon a red-sensitive silver halide e m ulsion layerggntaining, a s a cyanforming coupler, a member selected from the groupconsisting of phenolic and a-naphtholic cyan-forming couplers, eachhaving, at the para-position to the by droxyl group thereof, a memberselected from the group consisting of an iodine and a bromine atom, agreen-sensitive emulsion layer and a blue-sensitive emulsion layer, theimprovement which comprises said red-sensitive silver halide emulsionlayer being separated from said green-sensitive and said blue-sensitivesilver halide emulsion layers which it is in contact with by anintermediate layer positioned on at least one side of said red-sensitivesilver halide emulsion layer, said intermediate layer containing silverhalide grains whose photosensitivity is sufficiently low such that novisible image is formed therein by exposure and development of themulti-layer color photographic element and wherein said silver halidegrains of low photosensitivity are present only in said intermediatelayer.

2. A color photographic element as claimed in claim 1, wherein saidcyan-forming coupler is selected from compounds having the generalformula:

R @jm R1 wherein X is a member selected from the group consisting of aniodine atom and a bromine atom, R is a member selected from the groupconsisting of a hydrogen atom, an alkyl group, an aryl group, and R, isa ballasting organic radical containing at least eight carbon atoms.

3. A color photographic element as claimed in claim 1, wherein saidcyan-forming coupler is selected from compounds having the generalformula:

NHOOR:

wherein X is a member selected from the group consisting of an iodineatom and a bromine atom, R CO is an acyl group containing at least ninecarbon atoms, and R and R are each a member selected from the groupconsisting of a hydrogen atom, a halogen atom and an alkyl group.

4. A color photographic element as claimed in claim 1, wherein saidsilver halide which is incorporated in the intermediate layer isselected from the group consisting of silver chloride, silver bromide,silver chlorobromide, and silver iodobromide.

5. A color photographic element as claimed in claim 1 wherein the amountof said silver halide in said intermediate layer varies from 1 X10 to lX 10" mole per cm of said photographic element.

6. A color photographic element as claimed in claim 1 wherein saidsilver halide grains in said intermediate 9. A color photographicelement a'sih'i'ifiea'in claim 2 wherein said cyan-forming coupler isselected from the group consisting of:

I Br

CONHC zHu s nQ) C O NIICHiCHINCIIzCIhNI-IC O- O C 11H CONHCHaCHiNHC 0011cm K/ OaH on I H 01 NEC ocmoQcmm) CH; sHnU) Cl NHCONHCuHn

2. A color photographic element as claimed in claim 1, wherein saidcyan-forming coupler is selected from compounds having the generalformula:
 3. A color photographic element as claimed in claim 1, whereinsaid cyan-forming coupler is selected from compounds having the generalformula:
 4. A color photographic element as claimed in claim 1, whereinsaid silver halide which is incorporated in the intermediate layer isselected from the group consisting of silver chloride, silver bromide,silver chlorobromide, and silver iodobromide.
 5. A color photographicelement as claimed in claim 1 wherein the amount of said silver halidein said intermediate layer varies from 1 X 10 6 to 1 X 10 4 mole per 100cm2 of said photographic element.
 6. A color photographic element asclaimed in claim 1 wherein said silver halide grains in saidintermediate layer have a size of less than 0.5 micron.
 7. A colorphotographic element as claimed in claim 1 comprising a support havingcoated thereon, successively, said red-sensitive emulsion layer, saidintermediate layer, said green-sensitive emulsion layer and saidblue-sensitive emulsion layer.
 8. A color photographic element asclaimed in claim 1 comprising a support having coated thereon,successively, said blue-sensitive emulsion layer, said intermediatelayer, said red-sensitive emulsion layer, said intermediate layer andsaid green-sensitive emulsion layer.
 9. A color photographic element asclaimed in claim 2 wherein said cyan-forming coupler is selected fromthe group consisting of: